Toward benchmarking theoretical computations of elementary rate constants on catalytic surfaces: formate decomposition on Au and Cu.

With the emergence of methods for computing rate constants for elementary reaction steps of catalytic reactions, benchmarking their accuracy becomes important. The unimolecular dehydrogenation of adsorbed formate on metal surfaces serves as a prototype for comparing experiment and theory. Previously measured pre-exponential factors for CO formation from formate on metal surfaces, including Cu(110), are substantially higher than expected from the often used value of /, or ∼6 × 10 s, suggesting that the entropy of the transition state is higher than that of the adsorbed formate.